CA1062617A

CA1062617A - Hair dye and process for dyeing hair

Info

Publication number: CA1062617A
Application number: CA214,917A
Authority: CA
Inventors: Yoshimori Fujinuma
Original assignee: Shiseido Co Ltd
Current assignee: Shiseido Co Ltd
Priority date: 1973-12-01
Filing date: 1974-11-29
Publication date: 1979-09-18
Also published as: FR2252841A1; US3993436A; GB1460952A; JPS5147778B2; FR2252841B1; DE2455376A1; IT1056239B; DE2455376C3; JPS5088240A; DE2455376B2

Abstract

ABSTRACT OF THE DISCLOSURE
A novel hair dye is provided which does not cause allergic reactions and which has good colouring properties. The dye is based upon melanin precur-sors, which typically give rise to allergic reactions from many users. In the present invention, there is provided, as a cutting agent, a first component comprising dithiothreitol or dithioerythritol or both; as a dye composition, a second component comprising a conventional natural melanin precursor and at least one compound selected from the group consisting of 5-hydroxyindole 1 methyl-5,6-dihydroxyindole-2-carboxylate, tyramine, dopamine, 6-hydroxydopamine and pyrocatechol; as an oxidizing agent, a third component comprising a persulfate compound; and a further oxidizing agent consisting of tyrosinase which is ad-mixed with either said second or said third component.

Description

The present invention relates to hair dye for dyeing live hair and other keratinous fibers9 which are herein referred to as merely l1hair" for brevity's sake~ and more par-ticularly the present invention is concerned with a novel hypo-allergenic natural ha~r dye 7 the dyeing process OI which utilizes the forma-tion mechanism of natural melanin. The present invention also relates to a process for dyeing hair with said hair dye.
Heretofore9 hair has been conventionally dyed by permanent hair dyeing processes which are based on the conventional technique comprising the steps of oxidative polymerization of oxidizing azo dye stuffs including mainly p-phenylene diamine by action of hydrogen peroxide in the presence of alkali9 and penetrating and fixing the dye stuffs into hair keratin. However9 these processes i~ivolve some dangerD That is9 p-phenylene diamine type oxidizing dye which is a main component of the type of hair dyes used in these processes has a tendency to cause allergic reaction in the user.
In order to obviate the problem of allergic reaction various hair dyeing processes which utilize 'cyrosine9 DL-~-(3,4-dihydroxyphenyl)alanine (hereinafter referred to as l'DL-dopa"
for brevity's sake) or the like 5 as a precursor of natural melanin9 have been proposed instead of the aforementioned conventional hair dyeing processes. However, these hair dyeing processes have not prevailed as widely as might be expected. This is because there are some associated problems such as the stabilization of the melanin precursor and dyeing conditions to ensure both good dyeing effect and colour fastness~
The object of the present invention is to eliminate the aforementioned problems of the conventional hair dyes and to 3 provide a novel hair dye which is capable of dyein~ hair safely9 .~

. ,, , .. . , ,_i ~06~f~;17 with good colour fastness and with an even distribution of color.
Another object of the present invention is to provide a no~el hair dyeing process which enables hair to be dyed with better colour ~astness than the conventional process of utilizing the precursor of melanin.
Other objects ahd advantages of the present invention will be apparent from the following description.
In accordance with the present invention, there is provided a hair dye comprising a first dyeing composition including di-thiothreitol and/or dithioerythritol, a second dyeing compositionincluding (a) tyrosine and/or DL ~-(3,4-dihydroxyphenyl)alanine or its derivatives and (b) at least one compound selected from the group consisting of 5-hydroxyindole, methyl-5,6-dihydroxy-indole-2-carboxylate, tyramine, dopamine, 6-hydroxydopamine and pyrocatechol, a third dyeing composition including persulfate and/or tyrosinase which is compounded into said second-or third dyeiny composition.
In the present hair dye, the first dyeing composition includ-ing dithiothreitol (DT~) and/or dithioerythritol (DTE) acts as a cutting agent for the cystine-bond of hair to be dyed and, thus,.
melanin precursors can be effectively impregnated into keratin and fixed thereto. The melanin precursors used in the present dye are tyrosine and/or DL-dopa or its derivatives, which is compounded into said second dyeing composition. It has now been found that DTT and DTE can reduce the cystine-bond more effective-ly than mercaptans which are usually employed as the cutting agent for the cystine-bond in the conventional cold waving lotion, that ~ . - , . .

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.
10626~7 they can be r~adily rinsed with water from the hair to be treated due ~o their hydrophilic property derived from the presence of the hydroxyl group, and that they can effectively provide bonding positions of the precursors without disturbing - 3a -.
~, ; - , any oxidation reactions. Based on this observation9 a novel hair dye utilizing melanin precursors and having a high colour-fixing property can be obtained. For op-timum results9 it is preferred that the amount o~ DTT or DTE present in -'che first dyeing composi-tion be within the range of 0.5 - 3% by weight. When the amount of DTT or DTE is more than 3% by weight9 the hair being dyed is hurt and when the amount is less than 0.5~0 by weight9 colour fastness become worseO
Fig. 1 is an experimental graph ~ho~Jing comparative experi-mental results of dyeing property by the dif~erence of cuttingagen~s for hair dyeO
The above comparative experiments were carried out in the following manner. Woolswatches (white muslin cloth which9 a~ter dyeing9 is used for colour fastness tests based upon Japanese Industrial Standards L 0803)9 witll a size of 8 cm x 5 cm were dyed w;th DL-dopa in the presence of tyrosinase a-t 37-C for 1 hour and9 there~fter the woolswatches were shampooed and rinsed with luke-wari~ ~rater and dried. After drying9 the colour fastness of each dyed swatch was measured and the results are shown in Fig. 1.
In Fig. 19 A shows the result in the case ~here the cystine-bonc7 of tlle woolswatch being tested was not treated by a cutting agent 9 B shows the result in the case where the ~oolswatch being testecl was pre-treated with 2% by weight of thioglycollic acid solution in aqueous ammonium solution and C shows the result in the case where the woolswatch being tested was pre treated ~th 1.7% by weig7~ of dithiothreitol (DTT) solution in aaueous ammonium solu-tion. The measurements of the colour were ca~ried out by using a colour computer (Toshiba CC-l Type)~ X~Y and Z values of the dyed woolswatches thus obtained were converted to Hunter's L~a 3 and b chromaticity diagram indicating system and9 then9 the shade of the dyed cloths (S') was determined by the following equation (1) Sl = J 16(100 - L)2 + a2 + b2 .

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The values of S' thus obtained can be compared with each other in so far as hue is concerned, and it is true that as the S' value increases, the dyeing property becomes better.
As is apparent from the results shown in Fig~ 1., the result of C, which shows the S' value in the case where di-thiothreitol tDTT~ was employed as a cutting agent was better than the result of B in the case where thioglycollic acid was employed as in the conventional hair dye. Specifically, the S' value of C was 287 and that of B was 231. Of course the result of A, the case where no cutting agent was employed, was the worst of all.
The second dyeing composition according to the present in-vention comprises melanin precursors such as, for example DL-dopa, tyrosine or the like, and boosters for pigmentation such as, the derivatives of indoles or catechols, which considerably facilitate the fixation of the precursor into the hair. The boosters, according to the present invention, preferably include, for example, 5-hydroxyindole, methyl-5,6-dihydroxyindole-2-carb-oxylate, dopamine, 6-hydroxydopamine, pyrocatechol. tyramine and their related compounds. Heretofore, 5,6-dihydroxyindole or the like has been used as the lone dyeing component of a hair dye.
However, when it is used alone, sufficient hair dyeing effect cannot be obtained, and especially, it is not at all suitable for dyeing dark, stiff hair such as that of Japanese. It has now been found that colour fastness can be significantly ln-creased by using said boosters together with said melanin pre-cursors in a buffer solution of the pH within the range of 6.8 . . , ,: , . , ~ :. . .

.
~, . .

1 0 62 6~ 7 to 8Ø Further, in accordance with the present invention, it is possible to control the shade and the colour of the dyed hair to a fine degree by selecting the compounded substances or the compounding ratio of the melanin precursors and the boosters, and thus, any colour in the range of brown to black can be obtained. ~or optimum results, it is preferred that the amounts of the precursors and the boosters present in the second dyeing composition be within the range of approximately 0.4 -0 . 890 by weight and the range of approximately 0.3 - 3% by weight, respectively.
In the present hair dye, both tyrosin~ase and persulfate are used as the oxidizing agent. Persulfate used in the present hair dye includes, for example, ammonium persulfate and potassium persulfate. Since tyrosinase and persulfate are used in com-bination, as the oxidizing agent, in the present invention colour fastness of the present hair dye is considerably improved in comparison with that of the conventional hair dyeing composition using melanin precursors in which only tyrosinase is used as the oxidiæing agent. Thus, the cystine-bond which is cut by the action of DTT or DTE is effectively recombined and the dyed hair undergoes relatively little damage. Persulfate is compounded into the third dyeing composition of the present invention, and tyrosin~se can be compounded into the second or the third dyeing composition of the present invention. For optimum results, it is preferred that the amount of said persulfate present in the third dyeing composition be within the range approximately 1%

to lO~ by weight, and that the amount of said tyrosinase present .... .

in the second or third dyeing composition be within the range of approximately 0.1% to 1.0~ by weight.
The p~esent invention also including a hair dyeing process which comprises the steps of treating hair to be dyed with said first dyeing composition, then applying thereto said second dyeing composition and thereafter, embrocating the hair with said third dyeing composition.
In accordance with the preferred embodiment of the present invention, hair to be dyed is firstly treated with an aqueous 1~ ammonium solution of the first dyeing composition of the present invention for 10-15 minutes, the composition comprising DTT and/
or DTE, and a humectant, both dissolved in ammonium solution.
The humectant preferably includes sorbitol, 1,2-propylene glycol, polyethylene glycol, glycerol or the like, and it is preferred that the amount of the humectant in the first dyeing composition be within the range of approximately 0.5 - 5~ by weight. By treating hair to be dyed with the first dyeing composition, the cystine bond of the hair is effectively reduced. Secondly, the second dyeing composition in a phosphate buffer solution of pH
6.8 to 8.0 is applied to the hair for a sufficient time, for example about 30 - 60 minutes. During this application, a pene-trating agent such as polyoxyethylene (15)-nonyl-phenyl-ether, polyoxyethylene (20)-octylphenyl-ether, polyoxyethylene (20)-sorbitan-monolaurate or polyoxyethylene (40)-sorbitan-mono-stearate is preferably added into the second dyeing composition in order to facilitate the impregnation of the composition into the hair. For this purpose, it is also effective to mechanically ~ - 7 -., .
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rub the composition into the hair. The amount of the penetrating agent is preferably within the range of 2% and 3% by weight based upon the weight of the second dyeing composition. Further, into the second composition, in order to prevent the composition from dripping from the hair, a thickening agent such as water-soluble resins such as hydroxyethyl cellulose is compounded to give suitable viscosity to thé composition. Finally, the hair is embrocated with the third dyeing composition which comprises tyrosinase and persulfate such as, for example, ammonium per-sulfate or potassium persulfate. The tyrosinase and persulfateare compounded just before the third dyeing composition is to be used. The hair thus treated with the third - 7a -~.

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composition is allowed to stand for about 10 - 15 minutes and9 thereafter7 the hair is shampooed and rinsed with water. The tyrosinase may be compounded into the third composition or it may be compounded into the second composition just before the composi-tion is used.
The present invention now will be further illustrated bythe following examples. However 9 it should be understood that these are given merely to explain and not to limit the invention and that numerous changes may be made without departing from the spirit and the scope of the invention as hereinafter claimed.
In the examples, each aqueous amrnonium solution to be employed is a 8.5% by weight aqueous solution which is prepared by diluting a 29% by weight a~ueous ammonium solution with pure w~t,er. Further9 the tyrosinase to be used in each example is 500 units/mg of mushroom tyrosinase, and it is added to the second or the thircl composition to activate the composition just before the composition is used.
:~:{arlple The following three dyeing compositions were respectively prepared.
T'ne first dyeing composition was prepared by dissolving the following ingredients in lO0 ml of aqueous ammonium solutiono dithiothreitol .................. 1.0 g propylene glycol ................ 0.5 g ethylenediaminetetraacetic acid (as sodium s~lts) ......... 0.05 g The second dyeing cornposition was prepared by dissolving the following ingredients in 100 ml of a phosphate buffer solution of p~ 6.~ .
3 DL - dopa ............ 0.4 g ;l .
i ~ ~ .

L - tyrosine ........... Ø01 g ~``
5-llydroxyindole .~..... 0 0.5 g tyrosinase~ ............ Ø2 g hydroxyethylcellulose .. Ø 0.3 g * tyrosinase was dissolved just before the second dyeing composition was used for treating the hair to be dyed.
The third dyeing composition was prepared by dissolving 3,0g of ammonium persulfate in 50 ml of pure water.
The hair was treated with the first dyeing composition at ambient temperature for 15 minutes and9 thereafter, the treated hair was shampooed and rinsed with lukewarm water. Then~ the hair was treated with the second dyeing composition at ambient tempera-ture for 60 minutes. ~rther9 the treated hair was embrocated with t~e third dyeing composition for lO minutes. Thusg the hair was 5 dyed blac~, Example 2 The first dyeing composition was prepared by dissolving the following ingredients in lO0 ml of aqueous ammonium solution.
dithiothreitol ..0O.O 200 g propylene glycol ØO.O 5.0 g ethylenediaminetetraacetic acid (as sodium salts) ~o~ Ool g The second dyeing composition was prepared by dissolving the following ingredients in 100 ml of a phosphate buffer solution of pH 700 0 DL-dopa ................... ..Ø4 g 6-hydroxydopamine hydrochloride Ø.. 0.5 g tyrQsinase* ............ 0.. 0.3 g hydroxyethylcellulose ..... 0.5 g * tyrosinase was dissolved just before ~he second dyeing ,.. . . - .. , .. .. , ~ , . ~ . . . .
: , : . : .-. . . . . . .. - .

~O~;Z617 composition was usecl for treating the hair to be dyed.
The third dyeing composition was prepared by dissolving 3.0 g of a~monium persulfæte in 50 ml of pure water.
The hair was treated for 5 minutes with the first dyeing composition obtained above and9 thereafter9 the treated hair was shampooed and rinsed with lukewarm water. Then the hair was treated with the second dyeing composition for 60 minutes and9 thereafter9 the hair was embrocated with the third dyeing composition for 10 minutes. Thus, the hair was dyed black. In the above hair dyeing proced.ure 9 by changing the compounding molar ratio of DL-dopa to 6-hydroxydopamine hydrochloride in -the second dyeing composition9 irom 1 D 1 to 2 o 1 the hair was dyed from a reddish bro~ to a dark brown.
~xample 3 The first dyeing composition was prepared by dissolving the following ingredients in 100 ml of aqueous ammonium solution:
dithiothreitol 0...................... 0.5 g dithioerythritol ~.................... 1.0 g propylene glycol 0................ ,~. 2.0 g ethylenediaminetetraacetic acid (as sodium salts) .. 0........ 0.1 g ~, The second dyeing composition was prepared by dissolving the follo~Jing ingredients in 100 ml of a phosphate buffer solution of pH 8.0 o DL-dopa Ø............... 0.4 g ~opamine hydrochloride ... Ø 3O0 g tyrosinase* .............. 0.4 g hydroxyethylcellulose .... 0.5 g * tyrosinase was dissolved just before the second dyeing composition was used for treating the hair to be dyed.

. : .. .

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~le third dyeing composition was prepared by dissolving 3.0 g o~ ammonium persulfate in 50 ml of pure water.
The hair was treated with the first dyeing cornposition for 10 minutes and, thereafterg the treated hair was shampooed and rinsed with lukewarm water. Then9 the hair was treated with the second dyeing composition ~or 60 minutes9 and, further, the hair was embrocated with the third dyeing composition for 10 minutes.
Thus9 the hair was dyed black. In the above dyeing process, by chc~nging the compounding ratio of DL-dopa and dopamine in the second dyeing composition, the co~r of the hair was dyed ~rom a black to ~ dark bro~.
Example 4 The first dyeing composi~ion was prepared by dissolving the fol1owing ingredients in 100 ml o a~ueous ammonium solutiono dithiotl1reitol ............... 1.7 g propylene glycol .............. 2.0 g ethylenediamine tetraacetic acid (as sodium salts) ..... 0.1 g The second dyeing composition was prepared by dissolving -the following ingredients in 100 ml of a phosphate buffer solution o~ pH 8,0 0 DL-dopa ............. 0.4 g ~ .
tyramine hydrochloride ....... 1.5 g tyrosinase .O.,. 003 g hydroxyethylcellulose ~ ...... 005 g The third dyeing composition was prepared by dissolving 3.0 g of potassium persulfate in 50 ml of pure water.
The hair was dyed by using these three dyeing oompositions in the same manner as that of Example 3 and, thus9 the treated 30 hair was dyed dark brown.

.. . . .

~062617 EX~r,pl ~ 5 The first dyeing composition was prepared by dissolving the following ingredients in 100 ml of a~ueous ammonium solution:
dithioerythritol ............... 1.7 g propylene glycol ............... 2.0 g etl~lenediamine tetraacetic acid (as a sodium salts) ~ o ~ O o l ~, The second dyeing composition was prepared by dissolving the following ingredients in 100 ml of a phosphate buffer solution oi pH 6,8 o DL-dopa Ø..................... 0.4 g 5-hydroxyindole .Ø... 0.2 g pyrocatechol ~ O 0.2 g hydro~yethylcellulose ...O... O.5 g The third dyeing composition was prepared by dissolving o.L~ g OL tyrosinase and 3.0 g of ammonium persulfate in 50 ml of pure water. ;
The hair was treated for 10 minutes with the first dyeing composition prepared above and, thereafter, the treated hair was shampooed and rinsed with lukewarm water. Then, the second dyeing composition and the third dyeing composition were mixed together and9 immediately9 the ~ixture was sprinkled over the hair and9 thereafter9 the hair was embrocated for one hour. Thus9 the hair was dyed black.
Example 6 The ~irst dyeing composition was prepared by dissolving the ; iollowing ingredients in 100 ml o~ aqueous ammonium solution:
~ _r~orcaptoethanol ........... 2.0 g dithiothreitol ................. 0.5 g propylene glycol ............... 5.0 g ethylenediamine tetraacetic acid (as sodium salts) ..... O.lg ., -, . - . ,~ , ~ . , : .

~06Z~1'7 The second dyeing composition was prepared by dissolvtng the followLng ingredients in 100 ml of a phosphate buffer solution of pH 800 DL-dopa methylester hydrochloride ............ o.6 g pyrocatechol ............................... , 0.~ g metll~rl-5 9 6-dihydroxyindole-2-carboxylate~ . 0.01 g l1ydroxyethylcellulose .,... 0.5 g The third dyeing composition was prepared by dissolving 0.3 g of tyrosinase and 3.0 g of ammonium persulfate in 50 ml of pure wa-ter~
The hair was treated with these three dyeing compositions in the same manner as that of Example 5 and9 thus9 the treated hair was dyed brown.
Ex,arnple 7 This example illustrates the effect of the compounding ratio of the mel~nin precursor and the boosters for piC~mentation on the dyed colour.
Æach of eleven woolswatches (white muslin cloth used for colour fastness tests) with a size of 8 cm x 5 cm was pretreated '~, 20 with a 0.5% by weight DTT solution in a 8.5% by weight aqueous :
ammonium solution for 10 minutes. Then9 each of the treated woolswatches was dyed with a different second dyeing cornpositions as shown in Table 19 at 37C for 50 minutes in the presence of 10 mg of tyrosinase (500 units/mg) and~ thereafter9 each of the treated woolswatclles was further dyed by adding Ool g of ammo~ium persulfate for 10 minutes. Each of the dyed woolswatches was soaked in a 10%
shampooing solution for 5 minutes and shc~ken for 2 minutes and, thereafter, each of the dyed woolswatches was washed well with lukewarm water the temperature of which was about 40-C.

. - . -: . . . . . -' , ~ ,. : - :. . ::. . . . :.
.... ~ : .. . : .

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Table 1 , , _ _.

No. Dopa (mg) 5-hydroxyindole (mg) Pyrocatechol (mg) 1 50 _

2 40 10 _ 4 20 30 _ 6 10 40 _ 7 40 _ 10 8 30 _ 20 9 20 _ 30 _ 40 11 0 _ 50 _ Note: The ingredients listed in Table 1 were dissolved in 15 ml of a buffer solution of phosphoric acid (pH 6.8).
After drying, the colour of each dyed woolswatch was measured by using a colour computer. X, Y and Z values of the dyed woo~swatches thus measured were converted into Hunter's L, a and b chromaticity diagram indicating system and, then, the converted values of a and b were plotted in Fig. 2. Each number plotted in Fig. 2 indicates the same run No. in Table 1.
As shown in Fig. 2, in the case where the second dyeing composition of the present invention containing dope and 5-hydroxyindole in a phosphate buffer solution was used, i.e., run No. 1 through No. 6, as the compounded amount of 5-hydroxy-indole increased against the compounded amount of dope, it was observed - - . ::
. , - -: . . - -:
' ': -: :

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~062617 that the hue of the dyed woolswatch went from a gray through orange to red. On the other handy in the caæe where the seconc'~
clyeing composition containing dopa and pyrocatechol was used, i.e. run ~o. 7 through No. 11 9 as the compounded amount of pyrocatechol increased ~inst the compounded amo~nt o~ dopa, it can be observed from Fig. 2 that when the colour computer is used although the chroma of the dyed woolswatches is variecl9 the hue remains similar. However9 upon visual inspection the shade of the dyed woolswatch varies from a black to a dark-red.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In a hair dye based upon one or more of the group con-sisting of tyrosine and DL-.beta.-(3,4-dihydroxyphenyl) alanine or a derivative thereof as a precursor of natural melanin, the improve-ment which comprises:
as a cutting agent, 0.5-3% by weight of a first component comprising a compound or mixture of compounds selected from the group consisting of dithiothreitol and dithioerythritol;
as a dye composition, a second component comprising 0.4-0.8% by weight of said natural melanin precursor and 0.3-3%
by weight of at least one compound selected from the group consisting of 5-hydroxyindole, methyl-5,6-dihydroxyindole-2-carboxylate, tyramine, dopamine, 6-hydroxydopamine and pyrocathechol;
as an oxidizing agent, 1-10% by weight of a third component comprising a persulfate compound; and 0.1-1.0% by weight of a further oxidizing agent consist-ing of tyrosinase which is admixed with either said second or said third component.

2. The hair dye of Claim 1, wherein said persulfate is ammonium persulfate or potassium persulfate.

3. A hair dye comprising 0.5-3% by weight of a first dyeing component which is a compound selected from the group consisting of dithiothreitol and dithioerythritol;
a second dyeing component which comprises 0.4-0.8% by weight of (a) a compound selected from the group consisting of tyrosine, DL-.beta.-(3,4-dihydroxyphenyl) alanine, and the methyl ester of the latter compound, and (b) 0.3-3% by weight of a compound selected from the group consisting of 5-hydroxyindole, methyl-5, 6-dihydroxyindole-2-carboxylate, tyramine, dopamine, 6-hydroxy-dopamine and pyrocatechol;
1-10% by weight of a third dyeing component which is a persulfate selected from the group consisting of ammonium persul-fate and potassium persulfate, and; said hair dye further comprising 0.1-1.0% by weight of tyrosinase in combination with said second or third dyeing component: and said first, second and third compo-nents being in combination with an aqueous carrier.

4. The hair dye as claimed in Claim 1 or Claim 3 wherein said first component is present in an aqueous ammonium solution.

5. The hair dye as claimed in Claim 1 or Claim 3 wherein said second dyeing component is in a phosphate buffer solution of pH 6.8 to 8Ø